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TWI311126B - Nano-array and fabrication method thereof - Google Patents

Nano-array and fabrication method thereof Download PDF

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Publication number
TWI311126B
TWI311126B TW095136212A TW95136212A TWI311126B TW I311126 B TWI311126 B TW I311126B TW 095136212 A TW095136212 A TW 095136212A TW 95136212 A TW95136212 A TW 95136212A TW I311126 B TWI311126 B TW I311126B
Authority
TW
Taiwan
Prior art keywords
nano
substrate
polymer
forming
nano array
Prior art date
Application number
TW095136212A
Other languages
Chinese (zh)
Other versions
TW200724479A (en
Inventor
Chih-Chiang Chao
Po-Ling Shiao
Mei-Chun Lai
Original Assignee
Ind Tech Res Inst
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ind Tech Res Inst filed Critical Ind Tech Res Inst
Priority to TW095136212A priority Critical patent/TWI311126B/en
Publication of TW200724479A publication Critical patent/TW200724479A/en
Application granted granted Critical
Publication of TWI311126B publication Critical patent/TWI311126B/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B17/00—Methods preventing fouling
    • B08B17/02—Preventing deposition of fouling or of dust
    • B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
    • B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/021—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0016—Lenses

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Description

J311126 九、發明說明： . 【發明所屬之技術領域】 ， 本發明有關於一種奈米陣列的形成方法’而特別有關 - 於—種以壓印的方式形成奈米陣列的方法。 【先前技術】 規則性的奈米結構表面具有特殊的功效，例如具有超低反 射率蛾眼的複眼結構，抗灰塵沾附的昆蟲翅膀結構，疏水自清 ί 潔蓮花葉面的蓮花效應(lotus effect)等，尺度約1 〇〇nm左右的 結構具有特殊的性質，如何將這些奈米結構的功能應用在日常 ， 生活上，是現在奈米製程技術發展的目標。一般高分子想要達 • 到疏水自清潔、抗油或降低反射率等功能’必須藉由二次的表 面化學或物理處理以獲得上述的功能，在製程上相當複雜且價 格昂貴，且必須使用多種化學品或是附加的設備。以微影技術 為例’當圖案尺寸小於90nm時會有其製程限制，製程成本過 咼也不利於一般應用。 • c. G Bernhard( 1962)等人在 Acta Physiol Scand 雜諸中觀 祭飛蛾複眼在仪間對於光的南度敏感性，發現25〇nm直徑以 下近似圓錐的奈米結構在廣域波長範圍中具有超低的光反射 率，Clapham&Hutley 於 Nature(1973)上提出 Moth EyeJ311126 IX. INSTRUCTIONS: [Technical Field] The present invention relates to a method for forming a nano array, and is particularly related to a method for forming a nano array by imprinting. [Prior Art] The regular nanostructure surface has special effects, such as a compound eye structure with ultra-low reflectivity moth eyes, an insect wing structure resistant to dust, and a lotus effect of hydrophobic lotus leaves. Effects, etc., structures with a scale of about 1 〇〇 nm have special properties. How to apply the functions of these nanostructures to daily life and life is the goal of the development of nanometer process technology. In general, polymers want to achieve functions such as hydrophobic self-cleaning, oil resistance or reduced reflectivity. 'The secondary surface chemical or physical treatment must be used to obtain the above functions. It is quite complicated and expensive in the process, and must be used. A variety of chemicals or additional equipment. Taking lithography as an example, when the pattern size is less than 90 nm, there is a process limitation, and the process cost is too high for general applications. • c. G Bernhard (1962) et al. at Acta Physiol Scand, the mid-sensitivity of the moths to the light, and the nanostructure of the approximately conical nanometer below 25 〇nm in the wide-area wavelength range With ultra-low light reflectivity, Clapham & Hutley presented Moth Eye on Nature (1973)

Principle，W.barthlott等人在Planta雜誌上發表觀察到荷葉上 的疏水效果(lotus effect)，荷葉表面小於5〇nm的凸起結構，表 面奈米結構與水珠的接觸面積越小，越具有自清潔的功能。然 而’如何將這些功能實用化，R. C.Furneaux等在Nature發表 0424-A21293CIPTWF(N2)；P02940045TWC1；kelly 1311126 規則多孔性的氧化物薄膜(anodic alumina oxide, AAO)製作方 式，M. Steinhard等人在2002 science發表以此結構作為複製 模板，利用奈米孔洞侧壁浸潤的方式將溶融的高分子溶液吸附 或填入規格性奈米孔洞中，待溶劑揮發後，將奈米孔洞模板溶 解’剩下部分就為中空奈米管狀高分子，有人利用此方法製作 奈米纖維(美國專利20030089899)。 美國專利早期公開2004-0126305、2004-0013873利用上 述類似概念，先將奈米孔洞模板側壁鑛上一層材料，形成中空 奈米纖維，與導電基板結合後再填入内層材料，最後將模板蝕 刻除去，成為複合的奈米圓柱。以上三件專利皆以陽極氧化鋁 模板AAO作為複製用的模板來製作耐米纖維，無論是單一材 料或是内外層複合材料，在填充材料完全填滿模板後，都必須 將AAO模板蝕刻移除才能得到成形的纖維。 _ 侧專利KR細應㈣WGG Lee等人 AA〇模板 •為基礎，描述四種奈米結構的複製情況，其中將㈣極氧化成 籲乡孔性軌她結構，賴·情形不同，產生具有不同孔洞 =的域，將祕的高分子複製成型，賴板⑽除去後得 分子的奈米圓柱形結構，或是將模板上純結舰调偏丨Principle, W. Barthlott et al. published in Planta magazine the observation of the lotus effect on the lotus leaf. The surface of the lotus leaf is less than 5〇nm. The smaller the contact area between the surface nanostructure and the water droplet, the more Self-cleaning function. However, 'how to put these functions into practical use, RCFurneaux et al. published 0424-A21293CIPTWF (N2); P02940045TWC1; kelly 1311126 regular porous oxide film (AAO) in Nature, M. Steinhard et al. Science published this structure as a replication template, using the nanoporous sidewall infiltration method to adsorb or fill the molten polymer solution into the standard nanopore. After the solvent is volatilized, the nanoporous template is dissolved. As a hollow nano tubular polymer, a method has been used to produce nanofibers (U.S. Patent No. 20030089899). U.S. Patent Publication No. 2004-0126305, 2004-0013873 utilizes the similar concept described above to first form a hollow nanofiber by layering a material on the sidewall of the nanohole template, and then bonding the conductive substrate to the inner layer material, and finally etching the template. Become a composite nano cylinder. All of the above three patents use the anodized aluminum template AAO as a template for replication to make the resistant fiber. Whether it is a single material or an inner and outer composite, the AAO template must be removed after the filling material is completely filled with the template. In order to obtain the shaped fibers. _ Side patent KR fine (4) WGG Lee et al. AA〇 template • Based on the description of the replication of four nanostructures, which (4) is oxidized to the structure of the hole-like orbital, the Lai situation is different, resulting in different holes = In the domain, the secret polymer is replicated, the nano-cylindrical structure of the molecule is obtained after the removal of the plate (10), or the pure knot of the template is biased.

此專利除了以AAO本身結構作為 除去後的底板銘作為二次模板，同 0424-A21293CIPTWF(N2)；P02940045TWC1 ,)311126 樣是使用溶融的高分子溶液作為複製的材料，在高分子完全填 - 滿後必須除去溶劑，再將模板蝕刻移除並不能直接將模板與成 • 形的高分子膜片分開，在製程中會造成高分子結構上的變形， . 二次模板的奈米結構會與AAO模板的奈米結構差異過大，所 -複製出來的高分子模片奈米結構功能會有所不同，甚至被破壞 掉。 DE10154756中提出利用表層具有微結構氧化物鍍層作為 瞻奈米結構壓印的模板，進行奈米柱形體的壓模成型，模板本身 非中空型態利用molding方式可輕易製作表面具有規則性的奈 米結構，此方法所形成的奈米結構構型會與奈米模板一致，2 就疋完全複製模板的形狀，所以一種奈米模板僅一種奈米構 型，無法依製程條件調整構型的變化，且表層成型 士 料脆弱，在雌時若無介面處理，會將成㈣奈米結卿 • 毁，表面奈米結構無強化處理在使用時形成問題。 ，吴國專利早期公開綱麵74為高分子薄膜抗反射結構 _ >層1覆’在表面塗覆一層南反射微粒的表層，利用模具複製 的方式在表面形成波紋，硬化層塗覆在高分子膜片上，凹凸結 構與高反射率微粒結合，可以具有抗炫低反射的功能，此光學 功能層仍是藉由表面數十週期的波浪紋路與高折射粒子 斤、、且成’提供支撐的硬化層在光學功能層的下方，最底部才是 高分子膜片基板，多層的結構就會有介面折射率、接著強度的 問題’層與層之間不同的熱膨脹係數都必須加以考量，在環境 測》式與使用上都會需要特別去解決，所以製程困難度高，製程 成本也相對較高。 0424-A21293CIPTWF(N2)：P02940045TWC1 ；kelly Ί 1311126 【發明内容】 有鑑於此，本發㈣目的在於提供 陣列及其形成方法，具有快速成形程形奈米 等優點。 i釭間早、成本低廉 基 *該==的頂部具有…或二:體面成形’其 法，包括··=:=-種形成奈米陣列的方 具有複數個奈米孔洞；以補加 在n刀子基材上進行壓印製程； 、板 該高分子基材上形成複數個奈求凸起物。、^板脫版，在 在上述奈米陣列上可進一步形 為強化奈米陣列耐到性、韌機L機鍍層，作 及降低奈米陣列表面親疏水物理特性，以 層。㈣表面反料或增加表面親和力之軟硬質塗 【實施方式】 塑性念’可廣泛應用在熱 中，’而無須將高分子材/健融在有機溶劑 =保=未來溶劑去除以及溶劑揮發所導致的結構變形與 法^至第3 ®顯示本發明利用熱Μ式的奈米磨印方 的:：二孔性的陽極氧化紹為愿印模板，來形成奈 私圖。如第1圖所示，氧化_板⑻為純銘經過陽 0424-A2l293CIPTWF(N2)；P02940045TWC1；kelfy 1311126 • 極處理所形成，具有複數個奈米孔洞105，也可利用二次 陽極處理來增加奈米孔洞孔徑的均勻度，以精確控制壓印 製程後所形成的奈米陣列直徑的誤差，在一實施例中奈米 孔洞的直徑約小於200nm，較佳介於約20nm至150nm之 間。 如第2圖所示，先將高分子基材1〇3加熱至適當溫度使其 軟化，加熱溫度可視所使用之高分子種類不同而有所調整，其 中高分子基材103可為熱塑性高分子、熱固性高分子或UV固 化型高分子。其中較佳為熱塑性高分子例如：聚曱基丙烯酸曱 酯（polymethyl methacrylate，簡稱 PMMA)、聚碳酸酯 (polycarbonate ’ 簡稱 PC)、環狀烯烴共聚物（cyclo-olefin copolymers，簡稱 COC)、聚丙烯(p0lypr0pylene，簡稱 pp)、聚 乙烯(polyethylene ’ 簡稱 PE)、聚氯乙烯(p〇lyvinyl chloride，簡 稱 PVC)、聚乙烯對苯二甲酸醋(p〇iyethylene terephthalate，簡 稱PET)、液晶高分子(liquid crystal polymer，簡稱LCP)或熱塑 性聚亞醯胺（thermoplastic polymide，簡稱ΤΡΙ);熱固性高分 子例如為聚亞醯胺(polymide，簡稱ΡΙ)或環氧樹脂(Epoxy)。接 著可將高分子基材103向上朝氧化鋁模板iOi擠壓，或是將氧 化鋁模板101向下朝高分子基材1〇3擠壓進行壓印製程，使氧 化鋁模板101輕微陷入高分子基材1〇3中，使高分子基材1〇3 經擠壓進入模板複數個奈米孔洞105中，待壓印製程穩定 後冷卻，使高分子基材103收縮定型，之後導入界面處理劑， 直接將氧化鋁模板101與高分子基材1〇3施以外力分離，如第 3圖所示，在高分子基材1〇3上形成複數個奈米凸起物〖ο?， 0424-A21293CIPTWF(N2)；P02940045TWC1；kelly 9 .1311126 在-實施例中奈米凸起物107的直徑約2()至15Qnm，高度約 小於400mn，且其間距約小於50nm，高寬比約小於3。在一 較佳實施例中奈米凸起物107的高寬比約2。 如第3圖所示，進行脫模時不需處理高分子基材1〇3 的有機溶劑，可避免後續去除有機溶_，因溶劑揮發而 ‘致问刀子基材103上奈米陣列結構變形以及環保問題。 由於上述之壓印製程可直接以AA〇作為模板，與一般以微 影飯刻方式製作小於之奈料騎需之成本與製程 面積相比’具有相當的優勢，由上述壓印法在高分子基材 103淺層結構複製所形成的複數個奈米凸起物，深寬比約 小於3，且有別於傳統奈米纖維的製程，氧化銘模板1〇1 在屢印完成後’藉由親和力差異得以與高分子基材1〇3離 型，而不需賴刻的方式將氧化紹模板1()1去除。由於高 分子藉由孔洞介面附著力、加熱時流動高分子的内聚力， 以及成型後的收縮情形與製程真空度來控制奈米結構頂端 的不同型態’所以經由高分子材料塑化流變性調控、材料 選擇與製程條件設定，就可以翻不同微觀的奈米陣列結 構型態。 第5及第6圖顯示本發明—實施例中，藉由不同的製 程條件所形成之奈料列。使用Tg肖13()度的環狀稀煙 (Cyd〇-〇lefin)高分子材料’以奈米孔洞直徑小於觸腿的 AAO模板在15G度以及壓力小於l度小於_ 的情況下，可以形成如第5圖所示之奈米凸起物隐，其 頂部具有一弧形表面。另外，使用Tg㈣〇度的環狀稀烴 0424-A21 293CIPTWF(N2)；P02940045TWC1 ；kefly 1311126 ·、 ' (eydo-olefin)高分子材料以奈米孔洞直徑介於 100-200nm *的AA〇模板在152度以及壓力小於5bar，真空度大於latm 的’丨月形下，可以形成如第6圖所示之奈米凸起物107b，其 頂口P為凹〇 ’兩者之奈米結構高度不超過4〇Onm，其頂 端不同型態具有不同之功能，在物理上空氣與高分子介面 呈現比表面積分佈的情形，最頂端具有最小的接觸面積， 因此具有超同的接觸角、疏水特性與凡得瓦接觸力。此外， 若高分子基材103為-透明基材，與鍍層相接合，在小於 可見光波長的光學上具有折射率梯度的變化特性，具有降 低透明咼分子基材103表面反射率而提升光能利用率的效 - 果。 • 脫模後為了增加奈米結構（奈米凸起物107所形成的 奈米陣列）的強度’可在結構表面形成一順應性有機或無機 鑛層109,其厚度約為50nm至10// m，較佳約小於i〇〇nm， 如第4a及4b圖所示。其中該無機鍍層包括金屬，例如： Zr、Ti、Cu、Ag、Au、A卜 Ni、W、Fe 或 Pt ;氧化物， 藝例如：Si02、Ti02、ITO、GaAs、InGaAs、非晶矽或多晶 石夕，而有機鑛層包括聚砍氧烧(P〇lySil〇xane)、石夕、導電高 分子、有機發光一極體(organic light emitting diode，簡稱 OLED)、南分子發光二極體(p〇iymer light emitting diode ’ 簡稱 PLED)或聚二氧乙基嘆吩(p〇iyethylenedioxythiophene, 簡稱PEDOT)，用以增強奈米結構的韋刃性及耐刮性。傳統 上用來降低反射率之硬質塗層（hard coating)都是形成在光 學有效層的底層’而藉由本發明與高分子基材1〇3 —體成 0424-A21293CIPTWF(N2)；P02940045TWC1 ；kelly 1311126 • 形的奈米結構，其具有高分子材料的彈性強度，在其表面 形成之有機或無機鍍層109有如強化糖衣一般，可直接將 表面鍍層的強度顯現並具有修飾構形的效果，由於順應性 . 的形成在奈米結構表面，可使有機或無機鍍層109表現出 奈米結構的特殊構型。 第7a圖顯示本發明一實施例利用掃描式電子顯微鏡 觀察所得之奈米陣列微結構截面圖，在本實施例中利用氧 化鋁模板對透明之熱塑性高分子進行微壓印製程，壓印過 > 程中透明熱塑性高分子不完全填滿氧化鋁模板之奈米孔 洞，其中氧化鋁模板之奈米孔洞直徑約小於l〇〇nm，各孔 -洞間距約20nm，壓印成形脫模後的奈米結構截面圖如第 . 7a圖所示，奈米結構的深寬比約2，其結構頂端有如第6 圖所示之凹口。第7b圖為奈米陣列結構之上視圖，可看到 分佈均勻的奈米凸起物。 第8a圖顯示本發明另一實施例利用掃描式電子顯微 ' 鏡觀察所得之奈米陣列微結構截面圖，在本實施例中，利 I 用氧化鋁模板對透明之熱塑性高分子基材進行微壓印製 程，氧化鋁模板之奈米孔洞直徑約lOOnm，各孔洞間距約 50nm，壓印成形脫模後的奈米結構側視圖如第8a圖所示， 奈米結構的深寬比約3，結構頂端有如第5圖所示之弧形 表面，第8b圖為奈米結構之上視圖，可看到分佈均勻的奈 米陣列結構。 第9b圖顯示利用本發明之壓印製程在熱塑性高分子 基材上所形成之奈米陣列結構，與水所進行之接觸角量測 0424-A21293CIPTWF(N2)；P02940045TWC1 ；kelly 12 1311126 貫驗結果’尚分子基材表面與水的接觸& 鬥、、、巧144度，而望 9a圖顯示利用未經本發明壓印製程之熱塑性高分子美罘 行接觸角量測之結果’高分子基材表面與水觸 90度，由此可知，利用本發明氧化叙模板進行壓印戶 形成的奈米陣列結構’確實能達成如同荷葉之超疏：：： (lotus effect)。In addition to the structure of AAO itself, the patent is used as a secondary template. The same as 0424-A21293CIPTWF(N2); P02940045TWC1,) 311126, the molten polymer solution is used as the replication material, and the polymer is completely filled-filled. After the solvent has to be removed, the template is removed by etching and the template cannot be directly separated from the formed polymer film, which will cause deformation of the polymer structure during the process. The nanostructure of the secondary template will be associated with AAO. The difference in the nanostructure of the template is too large, and the function of the nano-structured polymer film will be different or even destroyed. In DE 10154756, it is proposed to use a surface layer with a microstructured oxide coating as a template for the sleek structure imprinting, and to perform a compression molding of a nano-column body. The template itself is non-hollow type, and the regular surface of the surface can be easily fabricated by means of molding. Structure, the nanostructure structure formed by this method will be consistent with the nano template, 2 will completely replicate the shape of the template, so a nano template has only one nano configuration, and the configuration change cannot be adjusted according to the process conditions. Moreover, the surface layer is weak, and if it is not treated by the interface in the female, it will be destroyed by the (four) nano-clearing, and the surface nanostructure has no strengthening treatment, which causes problems in use. , Wu Guo patent early disclosure profile 74 is a polymer film anti-reflective structure _ > layer 1 covered 'coated on the surface of a layer of southern reflective particles, using the mold to replicate the surface to form ripples, hardened layer coated in high On the molecular film, the concave-convex structure combined with the high-reflectivity particles can have the function of anti-glare and low reflection. The optical functional layer is still supported by the wavy lines and high-refractive particles of the surface for several tens of cycles. The hardened layer is below the optical functional layer, and the bottom is the polymer film substrate. The multilayer structure has the problem of interface refractive index and subsequent strength. The different thermal expansion coefficients between the layers must be considered. Environmental measurement and use will require special solutions, so the process is difficult and the process cost is relatively high. 0424-A21293CIPTWF(N2): P02940045TWC1; kelly Ί 1311126 SUMMARY OF THE INVENTION In view of the above, the present invention (4) aims to provide an array and a method for forming the same, which has the advantages of rapid forming process and the like. i 早 early, low cost base * The == top of the == or two: decent surface forming 'the method, including ··=:=- the kind of the nano-array formed has a plurality of nano-holes; The embossing process is performed on the n-knife substrate; and the plurality of nematic protrusions are formed on the polymer substrate. The plate is off-plate, and the nano-array can be further shaped to enhance the nano-array resistance, the coating of the L-machine, and to reduce the physical and hydrophobic properties of the surface of the nano-array. (4) Soft and hard coating with surface anti-reflection or increased surface affinity [Embodiment] Plasticity can be widely used in heat, 'without the need to polymerize/hardly melt in organic solvent=guarantee = future solvent removal and solvent evaporation Structural Deformation and Method ^ to 3 ® shows that the present invention utilizes a hot-spotted nano-spinning method: a two-porous anodizing process is used as a template to form a nanograph. As shown in Fig. 1, the oxidation_plate (8) is formed by pure yang 0424-A2l293CIPTWF (N2); P02940045TWC1; kelfy 1311126 • pole treatment, with a plurality of nanopores 105, which can also be increased by secondary anode treatment. The uniformity of the pore size of the nanopore to precisely control the error of the diameter of the nano-array formed after the imprinting process. In one embodiment, the diameter of the nanopore is less than about 200 nm, preferably between about 20 nm and 150 nm. As shown in Fig. 2, the polymer substrate 1〇3 is first heated to a suitable temperature to soften it, and the heating temperature may be adjusted depending on the type of the polymer to be used, wherein the polymer substrate 103 may be a thermoplastic polymer. , thermosetting polymer or UV curable polymer. Among them, preferred are thermoplastic polymers such as polymethyl methacrylate (PMMA), polycarbonate (PC), cyclo-olefin copolymers (COC), and polypropylene. (p0lypr0pylene, abbreviated as pp), polyethylene (polyethylene), polyvinyl chloride (p〇lyvinyl chloride, PVC), polyethylene terephthalate (PET), liquid crystal polymer ( Liquid crystal polymer (LCP) or thermoplastic polymide (referred to as ΤΡΙ); thermosetting polymer such as polymide (abbreviated as ΡΙ) or epoxy resin (Epoxy). Then, the polymer substrate 103 may be extruded upward toward the alumina template iOi, or the alumina template 101 may be pressed downward toward the polymer substrate 1〇3 to perform an imprint process, so that the alumina template 101 is slightly trapped in the polymer. In the substrate 1〇3, the polymer substrate 1〇3 is extruded into a plurality of nano-holes 105 of the template, and is cooled after the imprint process is stabilized, so that the polymer substrate 103 is contracted and shaped, and then the interface treatment agent is introduced. Directly separating the alumina template 101 from the polymer substrate 1〇3, as shown in FIG. 3, forming a plurality of nano bumps on the polymer substrate 1〇3 〖ο?, 0424- A21293CIPTWF(N2); P02940045TWC1; kelly 9.1311126 In the embodiment, the nanoprojection 107 has a diameter of about 2 () to 15 Qnm, a height of less than about 400 nm, and a pitch of less than about 50 nm and an aspect ratio of less than about 3. In a preferred embodiment, the nanoprojection 107 has an aspect ratio of about 2. As shown in Fig. 3, the organic solvent of the polymer substrate 1〇3 is not required to be processed during demolding, and the subsequent removal of the organic solvent can be avoided, and the nano-array structure deformation on the knife substrate 103 is caused by the solvent volatilization. And environmental issues. Since the above-mentioned imprint process can directly use AA〇 as a template, compared with the general cost of making a smaller amount of material than the process area by the lithography method, it has a considerable advantage, and the above-mentioned imprint method is used in the polymer. The plurality of nano-protrusions formed by the shallow structure replication of the substrate 103 have an aspect ratio of less than about 3, and are different from the process of the conventional nanofibers, and the oxidation template 〇1 is completed after the printing is completed. The affinity difference can be separated from the polymer substrate 1〇3, and the oxidized template 1()1 can be removed without etching. Since the polymer controls the different types of the top end of the nanostructure by the adhesion of the pore interface, the cohesive force of the flowing polymer during heating, and the shrinkage after molding and the process vacuum degree, the rheology is controlled by the plastic material, Material selection and process conditions can be set to different microscopic nano array structure types. Figures 5 and 6 show the columns of the present invention formed by different process conditions in the present invention. The use of a Tg Shaw 13() degree ring-shaped (Cyd〇-〇lefin) polymer material can be formed with an AAO template having a nanopore diameter smaller than the contact leg at 15 G degrees and a pressure less than 1 degree less than _ The nano-protrusion as shown in Fig. 5 has a curved surface at the top. In addition, the Tg (four) twist of the ring-shaped hydrocarbon 0424-A21 293CIPTWF (N2); P02940045TWC1; kefly 1311126 ·, '(eydo-olefin) polymer material with a nano-hole template diameter of 100-200nm * 152 degrees and pressure less than 5bar, vacuum degree is greater than lamm's 'moon shape, can form nano-protrusion 107b as shown in Figure 6, the top edge P is concave 〇 'the height of the nanostructure is not More than 4〇Onm, the different types of tops have different functions. Physically, the air and polymer interfaces exhibit a specific surface area distribution, and the top has the smallest contact area, so it has superb contact angle and hydrophobic characteristics. Get the contact force. Further, when the polymer base material 103 is a transparent substrate and bonded to the plating layer, it has a refractive index gradient change characteristic at a wavelength smaller than the visible light wavelength, and the surface reflectance of the transparent germanium molecular substrate 103 is lowered to enhance the light energy utilization. The effect of the rate - fruit. • After the demolding, in order to increase the strength of the nanostructure (nano array formed by the nanoprotrusions 107), a compliant organic or inorganic ore layer 109 may be formed on the surface of the structure, and has a thickness of about 50 nm to 10//. m, preferably less than about i〇〇nm, as shown in Figures 4a and 4b. Wherein the inorganic plating layer comprises a metal such as: Zr, Ti, Cu, Ag, Au, A, Ni, W, Fe or Pt; an oxide such as: SiO 2 , TiO 2 , ITO, GaAs, InGaAs, amorphous germanium or more The spar, and the organic ore layer includes polyoxane (P〇lySil〇xane), Shixi, conductive polymer, organic light emitting diode (OLED), and southern molecular light-emitting diode ( P〇iymer light emitting diode 'abbreviated as PLED) or p〇iyethylenedioxythiophene (PEDOT) is used to enhance the edge and scratch resistance of nanostructures. The hard coating conventionally used to reduce the reflectance is formed on the bottom layer of the optically effective layer, and by the present invention and the polymer substrate 1〇3 is formed into 0424-A21293CIPTWF(N2); P02940045TWC1; kelly 1311126 • Shaped nanostructure, which has the elastic strength of polymer materials. The organic or inorganic coating layer 109 formed on the surface is like a reinforced sugar coating. It can directly show the strength of the surface coating and have the effect of modifying the configuration. The formation of the properties on the surface of the nanostructure allows the organic or inorganic coating 109 to exhibit a particular configuration of the nanostructure. Fig. 7a is a cross-sectional view showing the microstructure of the nano-array obtained by scanning electron microscopy according to an embodiment of the present invention. In the present embodiment, the transparent thermoplastic polymer is micro-imprinted by an alumina template, and embossed &gt The transparent thermoplastic polymer in the process does not completely fill the nanopores of the alumina template, wherein the diameter of the nanometer pores of the alumina template is less than l〇〇nm, and the pore-hole spacing is about 20 nm, and the embossing is formed after demolding. The nanostructure cross-section is as shown in Fig. 7a. The nanostructure has an aspect ratio of about 2, and the top end of the structure has a notch as shown in Fig. 6. Figure 7b is a top view of the nanoarray structure showing a uniform distribution of nanoprojections. Fig. 8a is a cross-sectional view showing a microstructure of a nano-array obtained by scanning electron microscopy in another embodiment of the present invention. In the present embodiment, the transparent thermoplastic polymer substrate is coated with an alumina template. In the microimprint process, the diameter of the nanometer pores of the alumina template is about 100 nm, and the spacing of the holes is about 50 nm. The side view of the nanostructure after the embossing is released as shown in Fig. 8a, and the aspect ratio of the nanostructure is about 3 The top of the structure has an arc-shaped surface as shown in Fig. 5, and the 8b is a top view of the nanostructure, and a uniform array of nano-array structures can be seen. Figure 9b shows the nano-array structure formed on the thermoplastic polymer substrate by the imprint process of the present invention, and the contact angle measurement with water 0424-A21293CIPTWF(N2); P02940045TWC1; kelly 12 1311126 'The contact between the surface of the molecular substrate and the water is 144 degrees, and the 9a diagram shows the result of measuring the contact angle of the thermoplastic polymer without the embossing process of the present invention. The surface is exposed to water by 90 degrees, and it can be seen that the nano-array structure formed by the imprinter using the oxidized template of the present invention can achieve a lotus effect like: lotus effect.

第l〇a圖顯示本發明具有奈米陣列之高分子基材且有 壁虎腳效應（gecko ’ s effect)，可以將水珠鎖在具有奈米陣列 結構之高分子基材表面，水珠體積不超過1〇#L，而第i〇b 圖可以見到水珠被奈米表面抓住的情形。Figure l〇a shows a polymer substrate having a nano array of the present invention and having a gecko's effect, which can lock the water bead on the surface of the polymer substrate having a nano array structure, and the water droplet volume No more than 1〇#L, and the i〇b diagram can see the case where the water droplets are caught by the surface of the nanometer.

第11圖顯示一透明基板在可見光光譜之反射率，其中 區域A具有本發明之奈米凸起物’而區域b則不具有本發 明之奈米凸起物’如第11圖所示’在區域A光的反射輝 度比區域B低。在第11圖中的透明基板可為pC或c〇c， 以PC為例’區域A在可見光波長約為4〇〇〜7〇〇 nm之間 的反射率約為2〜3 ;以COC為例，區域a在可見光波長 約為400〜700 nm之間的反射率約為1〜2，不同的基板材 料其區域A的反射率更小。由此可得知，本發明之奈米陣 列不需導入色偏（color-shift)即可降低炫光及反射。 實驗研究顯示本發明之奈米凸起物實質上可增加高分 子基材與其上覆蓋鍍層之間的附著力，第12a及12b圖分 別顯示鑛在PC高分子基材上厚度為i〇0nm及2〇〇nm的 Au鍵層其附著力測試的結果。該附著力測試使用百格測試 法，其在具有鑛層之基材上切割出1 〇〇個方形的格子，並 0424-A21293CIPTWF(N2)；P02940045TWC1；kelly 13 •1311126 將3M膠f貼附於該格子上，然後快速剝除，殘留在基板 ‘上的格子數目提供附著力之相對百分比值。如第12a及12b ©所示，具有奈米凸起物之區域c通過百格測試，而不具 '有奈米凸起物之區域D則無法通過百格測試。值得注意的 是样明之奈米凸起物可用來改善任何有機或無機鑛層之 附著力’例如Si、Au、Cu等等，此外，pc基板以外的高 分子基板例如COC基板也可用在本發明中。 表一顯示利用本發明之壓印製程在透明熱塑性高分子 上所开>成之奈米陣列結構所進行之光反射率量測結果，利 用測定散色光的設備Hazemeter可測得一般透明熱塑性高Figure 11 shows the reflectance of a transparent substrate in the visible light spectrum, wherein the region A has the nanoprojection of the present invention and the region b does not have the nanoprotrusion of the present invention as shown in Fig. 11 The reflected light of the area A light is lower than the area B. The transparent substrate in FIG. 11 may be pC or c〇c, and PC is taken as an example. The reflectance of the region A at a visible light wavelength of about 4 〇〇 to 7 〇〇 nm is about 2 to 3; For example, the reflectance of the region a between visible light wavelengths of about 400 to 700 nm is about 1 to 2, and the reflectance of the region A of the different substrate materials is smaller. From this, it can be seen that the nano array of the present invention can reduce glare and reflection without introducing color-shift. Experimental studies have shown that the nanoprotrusions of the present invention substantially increase the adhesion between the polymer substrate and the overlying plating layer, and Figures 12a and 12b respectively show that the thickness of the ore on the PC polymer substrate is i 〇 0 nm and The results of the adhesion test of the 2 〇〇 nm Au bond layer. The adhesion test uses the Baige test method, which cuts 1 square square lattice on a substrate with a mineral layer, and 0424-A21293CIPTWF (N2); P02940045TWC1; kelly 13 • 1311126 attaches 3M glue f to On the grid, then quickly stripped, the number of grids remaining on the substrate 'provides a relative percentage of adhesion. As shown in Figures 12a and 12b ©, the area c with the nanoprotrusions passed the 100-gram test, and the area D with the 'nano bumps' failed to pass the 100-square test. It is worth noting that the nano bumps of the sample can be used to improve the adhesion of any organic or inorganic ore layer, such as Si, Au, Cu, etc. Further, a polymer substrate such as a COC substrate other than the pc substrate can also be used in the present invention. in. Table 1 shows the results of measurement of light reflectance by the embossing process of the present invention on a transparent thermoplastic polymer, and the Hazemeter for measuring scattered light can be used to measure a generally transparent thermoplastic high.

分子，例如塑膠膜片，之穿透率約92%，而在其表面以Z 發明之壓印製程所形成之奈米陣列結構，可使穿透率提升 至 94%。 表一 穿透率 傳統之透明熱塑性高分子 92.51 經本發明壓印製程之透明熱塑性高分子 94.18 經本發明壓印製程之透明熱塑性高分子 93.65 0424-A21293CIPTWF(N2)；P02940045TWC1 ：kelly 14 1311126 【圖式簡單說明】 ===本發明壓印製程之流程圖。 視圖 。 θ、下本發明實施例之奈米陣列結構的側 第5圖顯示本發明a 圖 月另一實施例之奈米陣列結構的側視 第6圖顯示本發明s 圖 月另1施例之奈米陣列結構的側視 第7a圖顯示本發明—a 所得之奈米陣顺結構之截面^烟附輪式電子顯微鏡觀察 第7b圖為第7a圖本半 第8a圖顯示本發明實' 列微結，之上視圖。 得之奈米陣狀微結構。W利崎描式電子顯微鏡觀察所 第8b圖顯示第8a圖岑 第9a圖顯示一般熱性、^^上視圖。 第_顯示本發明熱塑^1 子子之接觸角。 第l〇a圖顯示本發明執塑=八之接觸角。 對於水珠抓取功能之正視圖。回刀子基材表面壁虎腳效應 第纟《月熱塑性南分子基材表面壁虎腳效應對於水 珠抓取功能之侧視圖。 第11圖顯示可見光光譜的反射率。 第12a圖顯示在具有奈米凸起物及不具奈米凸起物之高 分子基材上錢錢100 nm厚的Au其附著力測試結果。 第12b圖顯示在具有奈米凸起物及不具奈米凸起物之高 0424-A21293CIPTWF(N2)；P02940045TWC1 ；kelly 15 1311126 分子基材上錢鍍200 nm厚的Au其附著力測試結果。 【主要元件符號說明】 101〜氧化銘模板； 103〜高分子基材； 105〜奈米孔洞； 107、107a、107b〜奈米凸起物； 108〜凹口； ► 109〜有機或無機鍍層； A、 C〜具有奈米凸起物之區域； B、 D〜不具奈米凸起物之區域。 0424-A21293CIPTWF(N2)；P02940045TWC1 ；kelly 16Molecules, such as plastic diaphragms, have a penetration rate of about 92%, and the nano-array structure formed by the imprint process of the Z invention on the surface can increase the transmittance to 94%. Table 1 Transmittance Conventional Transparent Thermoplastic Polymer 92.51 Transparent Thermoplastic Polymer 94.18 by Imprinting Process of the Invention Transparent Thermoplastic Polymer 93.65 0424-A21293CIPTWF(N2); P02940045TWC1: kelly 14 1311126 Description] === Flow chart of the imprint process of the present invention. View. θ, the side of the nano-array structure of the embodiment of the present invention, FIG. 5 shows a side view of the nano-array structure of another embodiment of the present invention. FIG. 6 shows the s of the present invention. Side view of the rice array structure Fig. 7a shows the cross section of the nano-parallel structure obtained by the present invention-a. The observation of the cigarette attached to the electron microscope is shown in Fig. 7b. Fig. 7a is a diagram showing the present invention. Knot, top view. The nano-shaped microstructure is obtained. W Lisaki Electron Microscope Observatory Figure 8b shows Figure 8a. Figure 9a shows the general thermal and ^^ top view. The first _ shows the contact angle of the thermoplastic ^1 sub-piece of the present invention. Figure l〇a shows the contact angle of the invention of the invention = eight. A front view of the water droplet capture function. The surface of the back surface of the knife substrate is the side view of the water-bead grabbing function. Figure 11 shows the reflectance of the visible light spectrum. Figure 12a shows the adhesion test results for Au with 100 nm thick Au on a high molecular substrate with nanoprotrusions and no nanoprojections. Figure 12b shows the adhesion test results of a 200 nm thick Au plated on a molecular substrate having a nanoprojection and a non-nano bump with a high 0424-A21293CIPTWF (N2); P02940045TWC1; kelly 15 1311126 molecular substrate. [Major component symbol description] 101~ Oxidation template; 103~ polymer substrate; 105~nano hole; 107, 107a, 107b~nano protrusion; 108~ notch; ► 109~ organic or inorganic coating; A, C~ areas with nanoprotrusions; B, D~ areas without nano-protrusions. 0424-A21293CIPTWF(N2); P02940045TWC1 ;kelly 16

Claims (1)

修正日期：98.4. I$111£ώ136212號申請專利範圍修正本 十、申請專利範圍： 1.一種奈米陣列，包括 一同分子基材，具有複數個奈米凸起物，鱼診 體成形，其中該奈米凸起物的頂部具有―凹/。…基材— 2.如申請專利範圍$ !項所述之奈米陣列， 材與該複數個奈米凸起物為相同材料。 、吞 3·如中請專利範圍第2項所述之奈米陣列，其中該言 好基材包括熱祕高分子、㈣性高分子或= 高分子。 、^如巾請專利範圍第3項所述之奈米陣列，其中該熱 塑性问分子包括 PMMA、PC、COC、PP、PE、PVC、pet、 LCP 或 ΤΡΙ 〇 5·如申請專利範圍第3項所述之奈米陣列，其中該熱 固性高分子包括ΡΙ或環氧樹脂(Epoxy)。 6. 如申請專利範圍第1項所述之奈米陣列，其係作為 自清潔膜。 7. 如申請專利範圍第1項所述之奈米陣列，其係作為 抗反射膜基板。 8. 如申請專利範圍第1項所述之奈米陣列，其係作為 吸附基板。 9·如申明專利範圍第丨項所述之奈米陣列，更包括一 有機或無機鍍層’·性地披覆在錄材與賴數個奈米 凸起物之上。 10.如·申明專利範圍第9項所述之奈米陣列，其中該有 1311126 « V 機鍍層包括：聚矽氧烷、矽、導電高分子、OLED、PLED 或 PEDOT。 11. 如申請專利範圍第9項所述之奈米陣列，其中該無 機鍍層包括：Zr、Ti、Cu、Ag、Au、A卜 Ni、W、Fe、Pt、 Si〇2、Ti〇2、ITO、GaAs、InGaAs、非晶碎或多晶梦。 12. 如申請專利範圍第9項所述之奈米陣列，其中該有 機或無機鍍層之厚度為50nm至10 // m。 13. 如申請專利範圍第9項所述之奈米陣列，其係作為 披覆塗層。 14. 如申請專利範圍第9項所述之奈米陣列，其中該奈 米凸起物改善該高分子基材與該有機或無機鍍層之間的附 著力。 15. —種形成奈米陣列的方法，包括： 提供一模板，具有複數個奈米孔洞； 以該模板在一高分子基材上進行壓印製程，控制該模 •板之該些奈米孔洞的尺寸、間距以及該壓印製程的真空 度，使得該高分子基材不完全填滿該些奈米孔洞；以及 將該模板脫膜，在該基材上形成複數個奈米凸起物， 其中該些奈米凸起物的頂部具有一凹口。 16. 如申請專利範圍第15項所述之形成奈米陣列的方 法，更包括加入界面處理劑以利該模板脫膜。 17. 如申請專利範圍第15項所述之形成奈米陣列的方 法，其中該模板係由純鋁經過一或二次陽極處理所製得。 18. 如申請專利範圍第15項所述之形成奈米陣列的方. 18 . 1311126 » * ’ 法’更包括形成一順應性的有機或無機鐘層於該基材與該 複數個奈米凸起物上。 19. 如申請專利範圍第μ項所述之形成奈米陣列的方 法’其中該有機鍍層包括：聚矽氧烷、矽、導電高分子、 OLED、PLED 或 PEDOT。 20. 如申請專利範圍第18項所述之形成奈米陣列的方 法’其中該無機鍍層包括：Zr、Ti、Cu、Ag、au、A卜Ni、 W、Fe、Pt、Si02、Ti〇2、ITO、GaAs、InGaAs、非晶矽或 多晶矽。 、21.如申請專利範圍第18項所述之形成奈米陣列的方 法，其中該有機或無機鍍層厚度約小於l〇〇nm。 ' 22.如申請專利範圍f 15項所述之形成奈米陣列的方 法，其中該高分子基材包括熱塑性高分子、熱固性高分子 或UV固化型高分子。 23. 如申請專利範圍第22項所述之形成奈米陣列的方 • 法，其中該熱塑性高分子包括：PMMa、PC、coc、PP、 PE、PVC、PET、LCP 或 TPI。 24. 如申請專利範圍第22項所逃之形成奈米陣列的方 法，其中該熱固性高分子包括PI或環氧樹脂）。 19Amendment date: 98.4. I$111£ώ136212 Patent application scope revision Ten, the scope of patent application: 1. A nano array comprising a molecular substrate having a plurality of nanoprotrusions and a fish body formation, wherein The top of the nanoprotrusion has a "concave". ...substrate - 2. The nano array as described in the patent application scope is the same material as the plurality of nanoprotrusions. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; In the case of a nanometer array as described in claim 3, wherein the thermoplastic polymer molecule comprises PMMA, PC, COC, PP, PE, PVC, pet, LCP or 〇 · 5 as claimed in claim 3 The nano array, wherein the thermosetting polymer comprises ruthenium or epoxy resin (Epoxy). 6. The nano array according to claim 1, which is used as a self-cleaning film. 7. The nano array according to claim 1, which is used as an antireflection film substrate. 8. The nano array according to claim 1, which is used as an adsorption substrate. 9. The nano array according to the scope of claim 2, further comprising an organic or inorganic coating layered onto the recording material and the plurality of nano protrusions. 10. The nano array according to claim 9 of the patent scope, wherein the 1311126 «V machine coating comprises: polyoxane, germanium, conductive polymer, OLED, PLED or PEDOT. 11. The nano array according to claim 9, wherein the inorganic plating layer comprises: Zr, Ti, Cu, Ag, Au, A, Ni, W, Fe, Pt, Si〇2, Ti〇2 ITO, GaAs, InGaAs, amorphous or polycrystalline dreams. 12. The nano array of claim 9, wherein the organic or inorganic coating has a thickness of 50 nm to 10 // m. 13. The nano array according to claim 9 of the patent application, which is used as a coating. 14. The nano array of claim 9, wherein the nanoprojection improves the adhesion between the polymeric substrate and the organic or inorganic coating. 15. A method of forming a nano-array, comprising: providing a template having a plurality of nano-holes; and performing an imprint process on a polymer substrate to control the nano-holes of the mold plate The size, the spacing, and the degree of vacuum of the imprint process, such that the polymer substrate does not completely fill the nanopores; and the template is released, and a plurality of nano bumps are formed on the substrate. Wherein the tops of the nano bumps have a notch. 16. The method of forming a nano array according to claim 15 of the patent application, further comprising adding an interface treatment agent to facilitate release of the template. 17. The method of forming a nano array according to claim 15, wherein the template is obtained by subjecting pure aluminum to one or two anode treatments. 18. The method of forming a nano-array as described in claim 15 of the patent application. 18 . 1311126 » * 'Method' further includes forming a compliant organic or inorganic clock layer on the substrate and the plurality of nano-convex On the object. 19. The method of forming a nano-array as described in the scope of claim [n] wherein the organic plating layer comprises: polysiloxane, germanium, conductive polymer, OLED, PLED or PEDOT. 20. The method of forming a nano array according to claim 18, wherein the inorganic plating layer comprises: Zr, Ti, Cu, Ag, au, Ab Ni, W, Fe, Pt, SiO 2 , Ti 〇 2 , ITO, GaAs, InGaAs, amorphous germanium or polycrystalline germanium. 21. The method of forming a nano array according to claim 18, wherein the organic or inorganic plating layer has a thickness of less than about 10 nm. 22. The method of forming a nano array according to claim 15, wherein the polymer substrate comprises a thermoplastic polymer, a thermosetting polymer or a UV curable polymer. 23. The method of forming a nano array according to claim 22, wherein the thermoplastic polymer comprises: PMMa, PC, coc, PP, PE, PVC, PET, LCP or TPI. 24. A method of forming a nano array as escaped by claim 22, wherein the thermoset polymer comprises PI or epoxy resin). 19
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